TW201723048A - Cyclic olefin resin film - Google Patents

Abstract

The present invention provides a cyclic olefin resin film characterized by having, on at least one surface of a cyclic olefin resin film substrate, a cured coating of an active-energy-ray-curable composition containing as essential components an active-energy-ray-curable compound (A), and a hindered amine-based photostabilizer (B) which is at least one species selected from the group consisting of a hindered amine-based photostabilizer (B1) having a polymerizable functional group and a hindered amine-based photostabilizer (B2) having a hindered phenol group. Provided is a cyclic olefin resin film whereby high abrasion resistance can be imparted to the surface of a cyclic olefin resin film substrate, and a cured coating having excellent adhesion to the surface of the cyclic olefin resin film substrate can be formed without a primer layer, the adhesion thereof not decreasing even after exposure to intense light.

Description

Cyclic olefin resin film

The present invention relates to a cyclic olefin resin film having a cured coating film of an active energy ray-curable composition having high scratch resistance and excellent adhesion to a cyclic olefin resin film substrate.

The cyclic olefin resin film is excellent in transparency, low birefringence, low moisture absorption, heat resistance, electrical insulation, chemical resistance, etc., and is widely used in optical members, medical, packaging films, automobiles, semiconductors, and the like. . In particular, in the optical members, the diversification of units for use in liquid crystal displays or touch panels has been explored, replacing the polyethylene terephthalate (PET) and triacetyl cellulose (TAC) used in the past. A plastic film having a high transparency and a low hygroscopicity is used as a plastic film.

Further, since the cyclic olefin resin film is insufficient in surface hardness, it is damaged during processing, and in order to improve abrasion resistance and scratch resistance, it is considered to provide hardening of an active energy ray-curable composition on the surface thereof. A protective layer such as a hard coat layer of a coating film. However, since the cyclic olefin resin film has an alicyclic structure as its main structure, the surface of the film has a low polarity and a water contact angle of about 90°. Therefore, when the active energy ray-curable composition is applied, it is difficult to apply the film. The problem of low adhesion between the surface of the substrate and the surface of the cyclic olefin resin film substrate and the hard coat layer.

As a method of improving the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer, it is proposed to provide a modified olefin-based resin having a polar group as a main component on the surface of the cyclic olefin resin film substrate. After the undercoat layer, a method of applying an ionizing radiation-curable resin to harden it (for example, refer to Patent Document 1). In this method, the adhesion between the surface of the cyclic olefin resin film substrate and the hard coat layer can be improved, but the step of coating and drying the undercoat layer is increased, which further causes a problem of a decrease in yield and an increase in cost.

In addition, as a method of attaching a hard coat layer to the surface of a cyclic olefin resin film substrate without providing an undercoat layer, a hard coat film containing a curable composition having a (meth) acrylate having an alicyclic structure is proposed. It is used as a hard coat layer (for example, refer to Patent Document 2). In the case of using the curable composition, in order to sufficiently adhere the surface to the surface of the cyclic olefin resin film substrate, it is necessary to increase the ratio of the (meth) acrylate having an alicyclic structure. However, when the ratio of the (meth) acrylate having an alicyclic structure is increased, the crosslinking density of the cured coating film is lowered, and the scratch resistance of the surface of the cured coating film is insufficient.

In addition, the adhesion (initial adhesion) immediately after the formation of the cured coating film of the active energy ray-curable composition on the surface of the cyclic olefin resin film substrate is high, but thereafter, when exposed to strong light, adhesion occurs. The decrease in properties (light adhesion) is a problem.

Here, it is desired to form a hard coat film having excellent adhesion to the surface of the cyclic olefin resin film substrate without imparting a high scratch resistance to the surface of the cyclic olefin resin film substrate, and without a primer layer. A cyclic olefin resin film of a cured coating film of an active energy ray-curable composition which does not have a decrease in adhesion after exposure to strong light.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2004-284158

Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-89458

Summary of invention

The problem to be solved by the present invention is to provide a cyclic olefin resin film which has high scratch resistance to the surface of a cyclic olefin resin film substrate and which can be provided without a primer on the surface of a cyclic olefin resin film substrate. A cured coating film having an excellent adhesion-producing hard coating film and an active energy ray-curable composition whose adhesion is not lowered after exposure to strong light is formed.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific light stabilizer is used in an active energy ray-curable composition as a material of a cured coating film formed on the surface of a cyclic olefin resin film substrate. It is possible to impart a high scratch resistance to the surface of the cyclic olefin resin film substrate, and to form a hard coating film having excellent adhesion between the surface of the cyclic olefin resin film substrate and the adhesion without primer. The invention is not reduced after exposure to glare, thereby completing the present invention.

That is, the present invention relates to a cyclic olefin resin film characterized by having a cured coating film of an active energy ray-curable composition on at least one side of a cyclic olefin resin film substrate, the active energy ray The curable composition contains an active energy ray-curable compound (A) and a hindered amine-based light stabilizer (B) as a main component, and the hindered amine-based light stabilizer (B) is selected from the group consisting of polymerizable functional groups. At least one of the group of the hindered amine light stabilizer (B1) and the hindered amine light stabilizer (B2) having a hindered phenol group.

The cyclic olefin resin film of the present invention has high scratch resistance by a hard coating film of an active energy ray-curable composition formed on the surface thereof, and a cured coating film and a cyclic olefin resin as a substrate It has high adhesion and its high adhesion will not decrease after exposure to strong light. Therefore, the cyclic olefin resin film of the present invention can be used as an optical film for use in liquid crystal displays and touch panels.

Form for implementing the invention

The cyclic olefin resin film of the present invention is a cured coating film having an active energy ray-curable composition on at least one surface of a cyclic olefin resin film substrate, and the active energy ray-curable composition contains active energy ray hardening. The compound (A) and the hindered amine light stabilizer (B) are mainly selected from the group consisting of a hindered amine light stabilizer (B1) containing a polymerizable functional group and having At least one of the group of hindered phenol-based hindered amine light stabilizers (B2).

The active energy ray-curable compound (A) may, for example, be a polyfunctional (meth) acrylate (A1) or a urethane (meth) acrylate (A2). These may be used alone or in combination of two or more.

In the present invention, the term "(meth)acrylate" means either or both of an acrylate and a methacrylate, and the term "(meth)acryloyl) means a propylene group and One or both of the methacrylonitrile groups.

The above polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acrylonitrile groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (A1) include 1,4-butanediol di(meth)acrylate and 3-methyl-1,5-pentanediol di(A). Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylic acid Ester, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. Di(meth)acrylic acid of (meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, ginseng (2-hydroxyethyl) isocyanurate Ester, di(meth) acrylate of diol obtained by adding 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, to 1 mole Bisphenol A addition of 2 moles of di(meth) acrylate of diol derived from ethylene oxide or propylene oxide Trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, Di-trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, gin(2-(methyl)acryloxyethyl)iso-cyanuric acid Ester, neopentyl alcohol tris(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta (methyl) ) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These polyfunctional (meth) acrylates (A1) may be used alone or in combination of two or more. Further, among these polyfunctional (meth) acrylates (A1), from the viewpoint of improving the scratch resistance of the cured coating film of the active energy ray-curable composition used in the present invention, it is preferably dipentaerythritol. Alcohol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol tri (meth) acrylate, more preferably Dipentaerythritol hexa(meth) acrylate is used in combination with dipentaerythritol penta (meth) acrylate. Further, as a mass ratio in the case where dipentaerythritol hexa(meth)acrylate is used in combination with dipentaerythritol penta(meth)acrylate, the scratch resistance of the cured film is improved. The range of 40/60~80/20 is better, the range of 50/50~75/25 is better, and the range of 60/40~70/30 is better.

The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate having a hydroxyl group (a2-2).

The polyisocyanate (a2-1) is an aliphatic polyisocyanate and an aromatic polyisocyanate, but the color of the cured coating film which can further reduce the active energy ray-curable composition used in the present invention is more It is preferably an aliphatic polyisocyanate.

The aliphatic polyisocyanate is a compound composed of an aliphatic hydrocarbon other than the isocyanate group. Specific examples of the aliphatic polyisocyanate include hexamethylene diisocyanate and An aliphatic polyisocyanate such as an amino acid diisocyanate or an isocyanuric acid triisocyanate; a decane diisocyanate, an isophorone diisocyanate, a methylene bis(4-cyclohexyl isocyanate), a 1,3-bis (isocyanate) An alicyclic polyisocyanate such as cyclomethyl, cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane or 2-methyl-1,5-diisocyanatocyclohexane Wait. Further, a trihydric body in which the above aliphatic polyisocyanate or alicyclic polyisocyanate is quantified can also be used as the above aliphatic polyisocyanate. Further, these aliphatic polyisocyanates may be used alone or in combination of two or more.

Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate of a diisocyanate which is a linear aliphatic hydrocarbon is preferred, and is alicyclic. Decanoic diisocyanate, isophorone diisocyanate of diisocyanate.

The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryl fluorenyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl ( Methyl) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono(meth) acrylate, 1,6-hexanediol mono(meth) acrylate, neopentyl Mono(meth)acrylate of glycol such as diol mono(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(methyl) Acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meth) acrylate, glycerol II ( a mono- or di(meth)acrylate of a triol such as methyl)acrylate or bis(2-(meth)acryloxyethyl)hydroxyethyl isocyanurate, or a part of an alcoholic hydroxyl group modified with ε-caprolactone and having a hydroxyl group of mono- and di(meth)acrylate; pentaerythritol tri(meth)acrylate, di-trimethylolpropane tri a compound having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryl fluorenyl group such as methyl acrylate or dipentaerythritol penta (meth) acrylate, or the compound is further ε-hexyl Lactone modified polyfunctional (meth) acrylate having hydroxyl group; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (meth) acrylate having an oxyalkylene chain such as ethylene glycol mono(meth)acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polybutylene oxide-polyoxidation (meth) acrylate having a block structure of oxyalkylene chain such as propylene mono(meth)acrylate; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly (Methyl) acrylate having a random structure of an oxyalkylene chain such as (propylene glycol-butanediol) mono(meth)acrylate. These (meth) acrylates (a2-2) may be used alone or in combination of two or more.

Among the aforementioned urethane (meth) acrylates (A2), in order to enhance the scratch resistance of the cured coating film of the active energy ray-curable composition used in the present invention, it is preferably in one molecule. A person having four or more (meth) acrylonitrile groups. In order to form the aforementioned urethane (meth) acrylate (A2) as having the above (meth) acrylate (a2-2), it has four or more (meth) acrylonitrile groups in one molecule. It is preferably one having two or more (meth) acrylonitrile groups. Examples of such a (meth) acrylate (a2-2) include trimethylolpropane di(meth)acrylate and ethylene oxide-modified trimethylolpropane di(meth)acrylic acid. Ester, propylene Alkyl modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(methyl)acryloxyethyl)hydroxyethyl isocyanuric acid Ester, pentaerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. One type of the (meth) acrylate (a2-2) may be used alone or two or more types may be used in combination with the above-mentioned aliphatic polyisocyanate. Further, among these (meth) acrylates (a2-2), pentaerythritol tri(meth) acrylate and dipentaerythritol penta (meth) acrylate are capable of improving scratch resistance. Preferably.

The reaction of the aforementioned polyisocyanate (a2-1) with the aforementioned (meth) acrylate (a2-2) can be carried out by a conventional urethanation reaction. Further, in order to promote the progress of the urethanization reaction, it is preferred to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane-based catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; and phosphorus compounds such as triphenylphosphine and triethylphosphine. An organotin compound such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate, or an organic zinc compound such as zinc octoate.

Further, as the active energy ray-curable compound (A) other than the above polyfunctional (meth) acrylate (A1) or urethane (meth) acrylate (A2), epoxy may be used. A higher molecular weight (meth) acrylate (A3) such as (meth) acrylate, polyester (meth) acrylate or polyether (meth) acrylate. The epoxy (meth) acrylate may, for example, be a bisphenol type epoxy resin, a novolac type epoxy resin, a polyepoxypropyl methacrylate or the like, and a (meth) group. acrylic acid The reaction is carried out to esterify the obtained one. In addition, as the polyester (meth) acrylate, for example, a polyester having a hydroxyl group at both terminals obtained by polycondensing a polycarboxylic acid and a polyhydric alcohol is reacted with (meth)acrylic acid. The esterified product may be obtained by reacting a polyvalent carboxylic acid with an alkylene oxide and reacting with (meth)acrylic acid to obtain an esterified product. Further, examples of the polyether (meth) acrylate include those obtained by reacting a polyether polyol with (meth)acrylic acid to carry out esterification. Further, the (meth) acrylate (A3) may be used singly or in combination of two or more.

In addition, in addition to the (A1) to (A3) exemplified as the active energy ray-curable compound (A), the active energy ray-curable composition used in the present invention has a phosphate group ( The methyl acrylate (A4) is preferred from the viewpoint of further improving the adhesion to the substrate. The aforementioned (meth) acrylate (A4) having a phosphoric acid group is a (meth) acrylate having at least one phosphate group in one molecule. Examples of the (meth) acrylate (A4) having a phosphoric acid group include (meth) propylene methoxyethyl phosphate, di(methyl) propylene methoxyethyl phosphate, and phosphoric acid tris (A). Further, a propylene methoxyethyl ester, a caprolactone-modified phosphoric acid (meth) propylene methoxyethyl ester, or the like may be used, and a compound having two or more (meth) acryloyl fluorenyl groups in one molecule may also be used. Further, these (meth) acrylates (A4) having a phosphoric acid group may be used alone or in combination of two or more.

In the case where the active energy ray-curable composition used in the present invention is blended with the (meth) acrylate (A4) having a phosphoric acid group, the blending amount thereof can further improve the adhesion to the substrate. In order to further improve the scratch resistance of the surface of the hardened coating film, it is preferred to be in the aforementioned active energy ray The curable compound (A) is from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass.

The active energy ray-curable composition used in the present invention contains, as a main component, the above-mentioned active energy ray-curable compound (A) and a hindered amine-based light stabilizer (B1) containing a polymerizable functional group. And at least one hindered amine light stabilizer (B) having a hindered phenol group-based hindered amine light stabilizer (B2).

The light stabilizer (B1) is, for example, a hindered amine light stabilizer having a polymerizable functional group such as a (meth)acryl fluorenyl group or a vinyl group. More specifically, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1,2,2,6,6-pentamethyl-4-piperidine Base (meth) acrylate and the like. These light stabilizers (B1) may be used alone or in combination of two or more. In this case, it is preferable to further improve the adhesion to the cyclic olefin resin and the adhesion after exposure to strong light (hereinafter, simply referred to as "light adhesion resistance"). 2,2,6,6-Tetramethyl-4-piperidinyl (meth) acrylate.

The light stabilizer (B2) is, for example, a hindered amine light stabilizer having a hindered phenol group such as a 3,5-di-tertiary butyl-4-hydroxyphenyl group. More specifically, a compound represented by the following formula (1) and the like can be given. This light stabilizer (B2) can also be used in combination with the aforementioned light stabilizer (B1).

The blending amount of the hindered amine light stabilizer (B) in the active energy ray-curable composition used in the present invention can further suppress the decrease in initial adhesion and light adhesion resistance to the cyclic olefin resin. The amount of the active energy ray-curable compound (A) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2% by mass, even more preferably 0.3 to 1.5% by mass, based on 100 parts by mass of the active energy ray-curable compound (A).

Further, the active energy ray-curable composition used in the present invention can be formed into a cured coating film by being applied to a ring-shaped base material and then irradiated with an active energy ray. The so-called active energy ray refers to ionizing radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, gamma rays, and the like. In the case where the ultraviolet ray is used as the active energy ray to form the cured coating film, it is preferred to add a photopolymerization initiator (C) to be described later to the active energy ray-curable composition of the present invention to improve the curability. Further, if necessary, a photosensitizer (D) may be further added to enhance the hardenability. On the other hand, in the case of using ionizing radiation such as electron beam, alpha ray, beta ray, gamma ray or the like, since the photopolymerization initiator (C) and the photosensitizer (D) are hardened without being used, Therefore, it is not necessary to add a photopolymerization initiator (C) or a photosensitizer (D) in particular.

The photopolymerization initiator (C) may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligo{2-hydroxy-2. -methyl-1-[4-(1-methylvinyl)phenyl]acetone}, diphenylethylenedione dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2 - Phytyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- An acetophenone compound such as phenylphenyl)-butanone; a benzoin compound such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide a mercaptophosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; diphenylethylenedione (biphenylformamidine), methylphenylacetaldehyde Ethyl ester, 2-(2-hydroxyethoxy)ethyl oxyphenylacetate, 2-(2-oxo-2-phenylethenyloxyethoxy)ethyl oxyphenylacetate, etc. Diphenylethylenedione compound; diphenyl ketone, o-benzylidene benzoic acid methyl-4-phenyldiphenyl ketone, 4,4'-dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4-Benzylmercapto-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)diphenyl ketone a diphenyl ketone compound such as 3,3'-dimethyl-4-methoxydiphenyl ketone, 2,4,6-trimethyldiphenyl ketone or 4-methyldiphenyl ketone ; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc. Ketone compound; Michelin, Aminodiphenyl ketone compound such as 4,4'-diethylaminodiphenyl ketone; 10-butyl-2-chloroacridone, 2-ethyl hydrazine, 9,10-phenanthrenequinone , camphorquinone, 1-[4-(4-benzylidenephenylhydrothio)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1 - Ketone and the like. These photopolymerization initiators (C) may be used alone or in combination of two or more.

In addition, examples of the photosensitizer (D) include a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-methylthiourea, and diethyldiamine. A sulfur compound such as sodium thiophosphate, s-benzylisothiouronium (isothiuronium)-p-toluenesulfonate or the like.

The photopolymerization initiator (C) and the photosensitizer (D) are used in an amount relative to the active energy ray-curable compound (A) and the aforementioned compound (B) in the active energy ray-curable composition of the present invention. The total amount is 100 parts by mass, preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10% by mass.

In addition to the active energy ray-curable compound (A) and the hindered amine-based light stabilizer (B), the active energy ray-curable composition of the present invention may be blended with an organic solvent depending on the use and required characteristics. Polymerization inhibitor, surface treatment agent, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, ultraviolet absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment An additive such as a dispersant or an organic bead; an inorganic filler such as cerium oxide (aragonite particle), aluminum oxide, titanium oxide, zirconium oxide or antimony pentoxide. These other blends may be used alone or in combination of two or more.

Among the inorganic fillers, by blending the vermiculite particles, the scratch resistance of the surface of the cured coating film of the active energy ray-curable composition used in the present invention can be further improved, and the adhesion to the substrate can be further improved. . As the foregoing vermiculite particles, those whose surface is modified by an organic surface may be used or those which have not been surface-modified. Further, the vermiculite particles further enhance the hard coat film of the active energy ray-curable composition used in the present invention. In terms of transparency and scratch resistance of the surface, it is preferably a nanometer order size vermiculite particle, more preferably a colloidal silica. The average particle diameter of the vermiculite particles is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm. Further, the average particle diameter is a value measured by a dynamic light scattering method.

In the case where the inorganic filler is blended, the blending amount thereof can further improve the scratch resistance of the surface of the cured coating film of the active energy ray-curable composition used in the present invention, and the adhesion to the substrate can be further improved. The amount of the active energy ray-curable compound (A) is preferably from 1 to 150 parts by mass, more preferably from 5 to 100 parts by mass, per 100 parts by mass of the active energy ray-curable compound (A).

The organic solvent is used to appropriately adjust the solution viscosity of the active energy ray-curable composition used in the present invention, and in particular, it is easy to adjust the film thickness in order to perform film coating. Examples of the organic solvent that can be used herein include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ethyl acetate, butyl acetate, and propylene glycol. An ester such as monomethyl ether acetate; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. These solvents may be used alone or in combination of two or more.

The cyclic olefin resin film substrate used in the cyclic olefin resin film of the present invention is not particularly limited as long as it is a cyclic olefin. A homopolymer may be used, and a copolymer may be used. For example, "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" manufactured by ZEON Co., Ltd.; "ARTON (registered trademark)" manufactured by JSR Co., Ltd. "TOPAS (registered trademark)" manufactured by Polyplastics Co., Ltd., etc.

The cyclic olefin resin film substrate is obtained by molding a cyclic olefin resin on a film. Moreover, in order to improve the adhesion to the cured coating film of the active energy ray-curable composition used in the present invention, the surface of the cyclic olefin resin film substrate is preferably a surface by a sand blast method or a solvent treatment method. Treatment by roughening treatment, electric treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone, ultraviolet light, electron beam irradiation treatment, oxidation treatment, etc. Among these, it is more preferable to perform electric treatment such as corona discharge treatment or normal piezoelectric treatment.

Further, the thickness of the cyclic olefin resin film substrate is preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 100 μm, still more preferably in the range of 10 to 50 μm. When the thickness of the film substrate is in this range, it is easy to suppress curling even in the case where the cured coating film of the active energy ray-curable composition used in the present invention is provided on one surface of the cyclic olefin resin film. .

The cyclic olefin resin film of the present invention is obtained by coating an active energy ray-curable composition on at least one surface of a cyclic olefin resin film substrate, and then irradiating an active energy ray to form a cured coating film. The method of applying the active energy ray-curable composition to the cyclic olefin resin film may, for example, die coating, micro gravure coating, gravure coating, roll coating, comma coating, or pneumatic blade coating ( Air knife coat), kiss coat, spray cloth, pass-over coating, dip coating, spinner coating, Wheeler coat, brush coating, use of wire mesh ( Silk screen), solid coat, wire bar coating, flow coat, and the like.

In addition, in the case where ultraviolet rays are used as the active energy ray to cure the active energy ray-curable composition, examples of the apparatus that emits ultraviolet ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and the like. A fusion lamp, a chemical lamp, a black light, a mercury-xenon lamp, a short arc lamp, a cadmium cadmium laser, an argon laser, a solar light, an LED, or the like.

The cyclic olefin resin film of the present invention is excellent in optical properties, dimensional stability, heat resistance, transparency, and scratch resistance on the surface of the substrate, and thus can be suitably used for various purposes, but as a liquid crystal display. An optical film of an image display unit of an image display device such as an (LCD) or an organic EL display (OLED) is particularly useful. In particular, since it has excellent scratch resistance even in a thin shape, it can be suitably used as, for example, miniaturization of electronic notes, mobile phones, smart phones, mobile audio players, mobile computers, tablet terminals, and the like. Or an optical film of an image display portion of an image display device that is required to be thinned and has a high demand. Further, when it is used as an optical film, it can be used as a protective film used for the outermost surface of the image display unit of the image display device or a substrate of the touch panel. Further, in the case of using a protective film, for example, in an image display device in which a transparent panel for protecting the image display module is provided on an upper portion of an image display module such as an LCD module or an OLED module, It is used by being attached to the surface or the inner surface of the transparent panel to effectively prevent scratches and to prevent scattering when the transparent panel is broken.

Example

The invention will be more specifically described below by way of examples.

(Preparation Example 1)

a mixture of dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA") and dipentaerythritol pentaacrylate (hereinafter abbreviated as "DPPA") (DPHA/DPPA=65/35 (quality) (1) 100 parts by mass of vermiculite particles ("MEK-ST40" manufactured by Nissan Chemical Industries, Ltd., average particle size 10 to 20 nm, 40% by mass of methyl ethyl ketone dispersed by organic vermiculite sol (citric acid) 25 parts by mass (10 parts by mass for vermiculite particles) and a hindered amine light stabilizer having a methacryl oxime group (ADK STAB (registered trademark) LA-87, manufactured by ADEKA Co., Ltd.); , 2,6,6-tetramethyl-4-piperidyl methacrylate) 1 part by mass, and 1-hydroxycyclohexyl phenyl ketone ("IRGACURE (registered trademark) 184", manufactured by BASF JAPAN Co., Ltd.) After 6 parts by mass of the mixture was uniformly stirred, it was diluted with methyl ethyl ketone to prepare an active energy ray-curable composition (1) having a nonvolatile content of 50% by mass.

(Preparation Example 2)

An active energy ray-curable composition (2) was prepared in the same manner as in Production Example 1 except that the blending amount of ADK STAB LA-87 was changed from 1 part by mass to 0.1 part by mass.

(Preparation Example 3)

The active energy ray-curable composition (3) was prepared in the same manner as in Production Example 1 except that the blending amount of ADK STAB LA-87 was changed from 1 part by mass to 0.5 part by mass.

(Preparation Example 4)

An active energy ray-curable composition (4) was prepared in the same manner as in Production Example 1 except that the blending amount of ADK STAB LA-87 was changed from 1 part by mass to 2 parts by mass.

(Preparation Example 5)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer having a methacrylonitrile group ("ADK STAB (registered trademark) LA-82" manufactured by ADEKA Co., Ltd.; 1, 2, An active energy ray-curable composition (5) was prepared in the same manner as in Production Example 1, except that 2,6,6-pentamethyl-4-piperidyl methacrylate.

(Preparation Example 6)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer having a hindered phenol group ("TINUVIN (registered trademark) PA144, manufactured by BASF JAPAN Co., Ltd.); represented by the following formula (1) The active energy ray-curable composition (6) was prepared in the same manner as in Production Example 1 except for the compound.

(Comparative Preparation Example 1)

An active energy ray-curable composition (R1) was prepared in the same manner as in Production Example 1 except that the ADK STAB LA-87 used in Preparation Example 1 was not used.

(Comparative Preparation Example 2)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 111FDL" manufactured by BASF JAPAN Co., Ltd.; dimethyl succinate and 4-hydroxy-2,2 a polymer of 6,6-tetramethyl-1-piperidineethanol with N,N',N",N'''-肆-(4,6-bis-(butyl-(N-methyl-)- 2,2,6,6-tetramethylpiperidin-4-yl)amino)-three Active energy ray hardening was carried out in the same manner as in Production Example 1, except that the mixture of -2-yl)-4,7-diazadecane-1,10-diamine (1:1 mass ratio) was used. Composition (R2).

(Comparative Preparation Example 3)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 770DF" manufactured by BASF JAPAN Co., Ltd.; bis(2,2,6,6-tetramethyl) An active energy ray-curable composition (R3) was prepared in the same manner as in Production Example 1, except that the 4-piperidinyl) sebacate.

(Comparative Preparation Example 4)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer (ADK STAB (registered trademark) LA-81, manufactured by ADEKA Co., Ltd.); bis(1-undecyloxy-2) An active energy ray-curable composition (R4) was prepared in the same manner as in Production Example 1, except that 2,6,6-tetramethylpiperidin-4-yl)carbonate was used.

(Comparative Preparation Example 5)

In addition to changing the ADK STAB LA-87 used in Preparation Example 1 to a hindered amine light stabilizer (manufactured by BASF JAPAN Co., Ltd.) In the same manner as in Preparation Example 1, except for "TINUVIN (registered trademark) 123"; decanedioic acid bis{2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl ester}) The active energy ray-curable composition (R5) was prepared.

(Comparative Preparation Example 6)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 5100" manufactured by BASF JAPAN Co., Ltd.; bis(2,2,6,6-tetramethyl) -1-(octyloxypiperidin-4-yl)-1,10-sebacate (bis(2,2,6,6-tetramethyl-1-octyloxypiperidin-4-yl)-1,10-decanedioate) With 1,8-bis[{2,2,6,6-tetramethyl-4-((2,2,6,6-tetramethyl-1-octyloxypiperidin-4-yl)-indole) An active energy ray-curable composition (R6) was prepared in the same manner as in Production Example 1, except that a mixture of alkane-1,10-diylpiperidin-1-yl}oxy]octane was used.

(Comparative Preparation Example 7)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer ("TINUVIN (registered trademark) 292" manufactured by BASF JAPAN Co., Ltd.; double (1, 2, 2, 6, 6 - 5) Methyl-4-piperidinyl) sebacate 70-80% by mass and methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate 20-30% by mass The active energy ray-curable composition (R7) was prepared in the same manner as in Production Example 1 except for the mixture.

(Comparative Preparation Example 8)

In addition, the ADK STAB LA-87 used in Preparation Example 1 was changed to a hindered amine light stabilizer (ADK STAB (registered trademark) LA-52, manufactured by ADEKA Co., Ltd.; 肆 (1, 2, 2, 6, 6) An active energy ray-curable composition (R8) was prepared in the same manner as in Production Example 1, except that pentamethyl-4-piperidinylbutane-1,2,3,4-tetraformate.

(Comparative Preparation Example 9)

The active energy ray curability was prepared in the same manner as in Preparation Example 1 except that the ADK STAB LA-87 used in Preparation Example 1 was changed to a UV absorber ("TLNUVIN (registered trademark) 400" manufactured by BASF JAPAN Co., Ltd.). Composition (R9).

(Comparative Preparation Example 10)

An active energy ray was prepared in the same manner as in Preparation Example 1 except that the ADK STAB LA-87 used in Preparation Example 1 was changed to a UV absorber ("TINUVIN (registered trademark) 384-2" manufactured by BASF JAPAN Co., Ltd.). Hardenable composition (R10).

(Comparative Preparation Example 11)

An active energy ray-curable composition was prepared in the same manner as in Preparation Example 1 except that the ADK STAB LA-87 used in Preparation Example 1 was changed to an antioxidant ("IRGANOX (registered trademark) 1010" manufactured by BASF JAPAN Co., Ltd.). (R11).

(Example 1)

The active energy ray-curable composition (1) obtained in Preparation Example 1 was applied to a surface having been subjected to electrical treatment (corona discharge treatment; output of 100 W, speed: 1.0 m/min) in advance using a wire bar (Wire Bar). A cyclic olefin resin film substrate ("ZEONOR (registered trademark) film ZF16-100" manufactured by Zeon Co., Ltd., thickness: 100 μm) was heated at 60 ° C for 90 seconds, and then an ultraviolet irradiation device (EYE GRAPHICS) was used in an air atmosphere. "MIDN-042-C1" manufactured by Co., Ltd., lamp: 120 W/cm, high-pressure mercury lamp), irradiated with ultraviolet light at an irradiation dose of 0.4 J/cm ^{2 to} obtain a cyclic olefin resin film having a cured coating film having a thickness of 2 μm (1) .

[Evaluation of scratch resistance]

For the surface of the cured coating film of the cyclic olefin resin film (1) obtained above, a crockmeter type friction tester (diameter 1.0 cm circular friction, steel wool # 0000 (Steel wool) was used. # 0000), load weight 500 g, 10 times back and forth) The test was performed to visually observe the surface of the cured coating film after the test, and the scratch resistance was evaluated by the following criteria.

A: There are no scars.

B: Less than 5 scratches.

C: 5 or less scars.

D: Multiple scars.

E: A number of obvious deep scars.

[Evaluation of initial adhesion]

On the surface of the cured coating film of the cyclic olefin resin film (1) obtained above, 11 slits in the vertical and horizontal directions were cut at intervals of 1 mm to prepare 100 squares. Next, a cellophane tape (Cellotape (registered trademark) CT-18, manufactured by NICHIBAN CO., LTD.) was attached to the surface thereof, and then peeled off in one go, and this operation was repeated twice. The initial adhesion was evaluated by the following criteria from the residual area ratio remaining without being peeled off. In addition, it is judged to be unacceptable if it is evaluated as D to F on the basis of the following criteria.

A: The residual area ratio is 100%.

B: The residual area ratio is 95% or more and 99% or less.

C: The residual area ratio is 85% or more and 94% or less.

D: The residual area ratio is 50% or more and 84% or less.

E: The residual area ratio is 35% or more and 49% or less.

F: The residual area ratio is 34% or less.

[Evaluation of adhesion (light adhesion resistance) after light resistance test]

With respect to the cyclic olefin resin film (1) obtained above, an accelerated weathering test by Sunshine Weather-O-Meter (according to JIS L0891, test conditions are as follows), after the test and the above The evaluation of the initial adhesion was performed in the same manner, and the light adhesion resistance was evaluated.

Light source: continuous illumination of sunlight carbon arc lamp

Temperature: 63 ° C

Relative humidity: 50% RH

Irradiation time: 48 hours

Rainfall cycle and time: not set

(Examples 2 to 6 and Comparative Examples 1 to 11)

In the same manner as in Example 1, except that the active energy ray-curable compositions (2) to (6) and (R1) to (R11) obtained in the above Preparation Examples 2 to 6 and Comparative Preparation Examples 1 to 11 were used. The cyclic olefin resin films (2) to (6) and (R1) to (R11) having the respective cured coating films were prepared, and the obtained cyclic olefin resin film was evaluated for scratch resistance, initial adhesion, and light adhesion resistance. Sex.

The composition of the active energy ray-curable composition prepared in the above Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 11 and the evaluation results of the cyclic olefin resin film obtained above are shown in Tables 1 to 3. Further, the compositions in Tables 1 to 3 are described in terms of nonvolatile content.

As a result of the evaluation shown in Table 1, in the examples 1 to 6 of the cyclic olefin resin film of the present invention, the surface of the cured energy-sensitive coating material having the active energy ray-curable composition of the film is excellent in scratch resistance, and The cyclic olefin resin film substrate has high initial adhesion, and is excellent in light adhesion resistance (adhesion after light resistance test).

On the other hand, Comparative Examples 1 to 11 shown in Tables 2 and 3 are cyclic olefin resin films having a cured coating film which does not contain the active energy ray-curable composition of the hindered amine light stabilizer used in the present invention. These cyclic olefin resin films are at least one of scratch resistance, initial adhesion, and light adhesion resistance, and have practical problems.

Claims (7)

A cyclic olefin resin film characterized by comprising a cured coating film having an active energy ray-curable composition on at least one surface of a cyclic olefin resin film substrate, wherein the active energy ray-curable composition contains an active energy ray-curable compound ( A) with a hindered amine light stabilizer (B) as a main component, the hindered amine light stabilizer (B) is selected from a hindered amine light stabilizer (B1) containing a polymerizable functional group, and At least one of the group of hindered amine light stabilizers (B2) having a hindered phenol group. The cyclic olefin resin film according to claim 1, wherein the light stabilizer (B1) is selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate and 1,2 At least one of the group of 2,6,6-pentamethyl-4-piperidinyl (meth) acrylate. The cyclic olefin resin film according to claim 1, wherein the light stabilizer (B2) is a compound represented by the following formula (1), The cyclic olefin resin film according to any one of claims 1 to 3, wherein the hindered amine light stabilizer (B) is contained in an amount of 0.05 to 100 parts by mass of the active energy ray-curable compound (A). A range of 5 parts by mass. The cyclic olefin resin film according to any one of claims 1 to 4, wherein the active energy ray-curable compound (A) is a polyfunctional (meth) acrylate (A1). The cyclic olefin resin film according to claim 5, wherein the polyfunctional (meth) acrylate (A1) is selected from the group consisting of dipentaerythritol hexa(meth) acrylate and dipentaerythritol penta (methyl) At least one of the group of acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. The cyclic olefin resin film according to any one of claims 1 to 6, wherein the active energy ray-curable composition further contains an inorganic filler.